EP2144959B1 - Elastic particle foam based on polyolefin/styrene polymer mixtures - Google Patents

Elastic particle foam based on polyolefin/styrene polymer mixtures Download PDF

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EP2144959B1
EP2144959B1 EP20080735092 EP08735092A EP2144959B1 EP 2144959 B1 EP2144959 B1 EP 2144959B1 EP 20080735092 EP20080735092 EP 20080735092 EP 08735092 A EP08735092 A EP 08735092A EP 2144959 B1 EP2144959 B1 EP 2144959B1
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EP
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Prior art keywords
polymer
weight
thermoplastic
particles
foam
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German (de)
French (fr)
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EP2144959A1 (en
Inventor
Carsten Schips
Klaus Hahn
Georg GRÄSSEL
Daniela Longo
Jens Assmann
Andreas Gietl
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BASF SE
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BASF SE
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Priority to PL08735092T priority patent/PL2144959T3/en
Priority to EP20080735092 priority patent/EP2144959B1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/10—Applying counter-pressure during expanding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249978—Voids specified as micro

Definitions

  • the invention relates to thermoplastic particle foams having cells of average cell size in the range of 20 to 500 microns, in which the cell membranes have a nanocellular or fibrous structure with pore or fiber diameter below 1500 nm, and to processes for their preparation.
  • Expandable polymer mixtures of styrene polymers, polyolefins and optionally solubilizers, such as hydrogenated styrene-butadiene block copolymers are, for example DE 24 13 375 . DE 24 13 408 or DE 38 14 783 known.
  • the foams obtainable therefrom are said to have better mechanical properties than foams of styrene polymers, in particular better elasticity and lower brittleness at low temperatures, and insensitivity to solvents such as ethyl acetate and toluene.
  • the propellant holding capacity and the foamability of the expandable polymer blends at low densities are not sufficient for processing.
  • the WO 2005/056652 describes particle foam moldings having a density in the range of 10 to 100 g / l, which are obtainable by welding prefoamed foam particles of expandable, thermoplastic polymer granules.
  • the polymer granules contain mixtures of styrenic polymers and other thermoplastic polymers and can be obtained by melt impregnation followed by pressurized underwater granulation.
  • elastic particle foams made of expandable interpolymer particles are known (eg. US 2004/0152795 A1 ).
  • the interpolymers are obtainable by polymerization of styrene in the presence of polyolefins in aqueous suspension and form an interpenetrating network of styrenopolymers and olefin polymers. From the expandable polymer particles, however, the blowing agent diffuses out quickly, so that they must be stored at low temperatures and only a short time have sufficient foamability.
  • the WO 2005/092959 describes nanoporous polymer foams obtainable from propellant-containing multiphase polymer blends with domains in the range of 5 to 200 nm.
  • the domains consist of a shell-shell particle obtainable by emulsion polymerization in which the solubility of the blowing agent is at least twice as high as in the adjacent phases.
  • the object of the present invention was to provide expandable, thermoplastic polymer particles with low blowing agent loss and high expansion capacity, which can be processed into particle foams with high rigidity and at the same time good elasticity, and a process for their preparation.
  • thermoplastic particulate foams Accordingly, the above-described thermoplastic particulate foams have been found.
  • thermoplastic particle foams preferably have cells of average cell size in the range of 50 to 250 microns and a nanocellular structure or a fibrous stretched, disperse phase structure in the cell walls of the thermoplastic particle foams with a mean pore or fiber diameter in the range of 10 to 1000 nm, especially preferably in the range of 100 to 500 nm.
  • FIG. 1 shows a section through the cells of a thermoplastic particle foam according to the invention.
  • FIG. 2 shows a 10x enlarged detail of the in FIG. 1 shown cell structure with a nanocellular cell wall.
  • the polymer matrix of the thermoplastic particle foams preferably consists of a continuous, styrene polymer-rich phase and a dispersed polyolefin-rich phase.
  • the polymer mixture in step b) can also be granulated first and the granules subsequently re-impregnated in the aqueous phase under pressure and elevated temperature with a blowing agent to form expandable thermoplastic polymer particles. These can then be isolated after cooling below the melt temperature of the polymer matrix or obtained directly by pressure release as prefoamed foam particles (stage c).
  • the polymer mixture having a continuous and a disperse phase can be prepared by mixing two incompatible thermoplastic polymers, for example in an extruder.
  • the polymer mixture preferably contains 45 to 98.9% by weight, particularly preferably 55 to 89.9% by weight of a thermoplastic polymer A), in particular styrene polymers such as standard (GPPS) or impact polystyrene (HIPS) or styrene-acrylonitrile copolymers (SAN) or acrylonitrile-butadiene-styrene copolymers (ABS).
  • GPPS standard
  • HIPS impact polystyrene
  • SAN styrene-acrylonitrile copolymers
  • ABS acrylonitrile-butadiene-styrene copolymers
  • Standard polystyrene types are particularly preferred having weight average molecular weights ranging from 120,000 to 300,000 g / mol and a melt volume rate MVR (200 ° C / 5 kg) according to ISO 113 in the range of 1 to 10 cm 3/10 min, for example PS 158 K, 168 N or 148 G of BASF Aktiengesellschaft.
  • MVR melt volume rate
  • the polymer mixture contains preferably 1 to 45 percent by weight, in particular 4 to 37 wt .-% of an incompatible with the thermoplastic polymer A), also thermoplastic polymer B).
  • polymer B) is preferably a polyolefin, for. B. homo- or copolymers of ethylene and / or propylene, in particular polyethylene used, in particular when a styrene polymer is used as the polymer A).
  • injection molding grades come as polypropylenes, such as Adstif® RA 748 T or impact types such as Clyrell® EM 2484 from Basell into consideration.
  • Suitable polyethylenes are commercially available homopolymers of ethylene, such as PE-LD (injection molding types), LLD, -HD, or copolymers of ethylene and propylene (for example Moplen® RP220 and Moplen® RP320 from Basell), ethylene and octene (Engage® ) or ethylene and vinyl acetate (EVA), polyethylene acrylates (EA) such as Surlyn® types 1901 and 2601 from DuPont or ethylene-butylene acrylates (EBA) such as Lucofin® 1400 HN, 1400 HM from Lucobit AG.
  • PE-LD injection molding types
  • LLD low density low density polyethylene
  • -HD low density polyethylene
  • copolymers of ethylene and propylene for example Moplen® RP220 and Moplen® RP320 from Basell
  • Engage® ethylene and octene
  • EVA ethylene and vinyl acetate
  • EA polyethylene acrylates
  • the melt volume index MVI (190 ° C / 2.16 kg) of the polyethylenes is usually in the range of 0.5 to 40 g / 10 min, the density in the range of 0.86 to 0.97 g / cm 3 , preferably in the range from 0.91 to 0.95 g / cm 3 .
  • PIB polyisobutene
  • compatibilizer for targeted adjustment of the desired morphology are usually compatibilizer (component C) in amounts of 0.1 to 10 wt .-%, preferably 3 to 8 wt .-%, based on the polymer matrix used.
  • the compatibilizer leads to improved adhesion between the polyolefin-rich and the polystyrene-rich phase and improves the elasticity of the foam even in small amounts compared to conventional EPS foams. Investigations of the domain size of the polyolefin-rich phase showed that the compatibilizer stabilized small droplets by reducing the interfacial tension.
  • the electron micrograph of a section through a blowing agent-containing, expandable polystyrene / polyethylene shows disperse polyethylene domains in the polystyrene matrix.
  • hydrogenated or unhydrogenated styrene-butadiene or styrene-isoprene block copolymers are suitable for this purpose.
  • the total diene content is preferably in the range from 20 to 60% by weight, particularly preferably in the range from 30 to 50% by weight, the total styrene content is correspondingly preferably in the range from 40 to 80% by weight, particularly preferably in the region of 50 to 70% by weight.
  • Suitable styrene-butadiene block copolymers which consist of at least two polystyrene blocks S and at least one styrene-butadiene copolymer block S / B, are, for example, star-branched block copolymers, such as those in EP-A 0654488 are described.
  • block copolymers having at least two hard blocks S 1 and S 2 of vinylaromatic monomers having at least one intermediate random soft block B / S of vinylaromatic monomers and diene are suitable, the proportion of hard blocks being more than 40% by weight, based on the total block copolymer and the 1,2-vinyl content in soft block B / S is below 20%, as in WO 00/58380 are described.
  • Suitable compatibilizers are linear styrene-butadiene block copolymers of the general structure S- (S / B) -S lying with one or more, between the two S blocks, a random styrene / butadiene distribution having blocks (S / B) random , suitable.
  • Such block copolymers are obtainable by anionic polymerization in a non-polar solvent with the addition of a polar cosolvent or a potassium salt, such as in WO 95/35335 respectively.
  • WO 97140079 described.
  • the vinyl content is understood to mean the relative proportion of 1,2-linkages of the diene units, based on the sum of the 1,2-, 1,4-cis and 1,4-trans linkages.
  • the 1,2-vinyl content in the styrene-butadiene copolymer block (S / B) is preferably below 20%, in particular in the range from 10 to 18%, particularly preferably in the range from 12 to 16%.
  • Preferred compatibilizers are styrene-butadiene-styrene (SBS) triblock copolymers having a butadiene content of from 20 to 60% by weight, preferably from 30 to 50% by weight, which may be hydrogenated or unhydrogenated.
  • SBS styrene-butadiene-styrene
  • These are for example under the name Styroflex® 2G66, Styrolux® 3G55, Styroclear® GH62, Kraton® D 1101, Kraton® G 1650, Kraton® D 1155, Tuftec® H1043 or Europren® SOL 6414 commercially.
  • SBS block copolymers with sharp transitions between B and S blocks.
  • An improvement in compatibility can be achieved additionally by hydrogenating the butadiene blocks, for. B. Kraton® G types.
  • additives may be added to the multiphase polymer mixture in amounts that do not interfere with the domain formation and resulting foam structure.
  • polyolefin waxes or talc may additionally be added in amounts of 0 to 5, preferably 0.5 to 3 wt .-%, based on the polymers A) to C).
  • blowing agent (component D) in step b) preferably 1 to 15 weight percent, preferably 3 to 10 weight percent, based on the polymer mixture A) to C) of a physical blowing agent, such as aliphatic C 3 to C 8 hydrocarbons, alcohols, ketones , Ethers or halogenated hydrocarbons used. Preference is given to using isobutane, n-butane, isopentane, n-pentane or isohexane.
  • Suitable co-propellants are those having a lower selectivity of solubility for the domain-forming phase, for example, gases such as CO 2 , N 2 , fluorocarbons or noble gases. These are preferably used in amounts of from 0 to 10% by weight, based on the polymer mixture.
  • the propellant loaded melt may then be extruded through a corresponding die into foam sheets, strands or particles and cut.
  • the melt emerging from the nozzle can also be cut directly into expandable or selectively foamed polymer particles.
  • the setting of the appropriate backpressure and a suitable temperature in the water bath of the UWG thus allows a targeted production of foam particles to allow.
  • the expandable polymer particles In order to produce the expandable polymer particles, underwater granulation is generally carried out at pressures in the range from 1.5 to 10 bar.
  • the nozzle plate usually has several nests with several holes. With a hole diameter in the range of 0.2 to 1 mm, expandable polymer particles having the preferred mean particle diameter in the range of 0.5 to 1.5 mm.0.8 mm are obtained. Expandable polymer particles with narrow particle size distribution and an average particle diameter in the range of 0.6 to 0.8 mm lead to a better filling of the molding machine with filigree molding design. Furthermore, this achieves a better molding surface with less gusset volume.
  • the resulting round or oval particles are foamed to a diameter in the range of 0.2 to 10 mm. Its bulk density is preferably in the range of 10 to 100 g / l.
  • the average diameter of the disperse phase of the polymer mixture prepared in step a) is preferably in the range from 1 to 2000 nm, particularly preferably in the range from 100 to 1500 nm.
  • the final expandable thermoplastic polymer particles may be coated by glycerol esters, antistatic agents or anticaking agents.
  • the welding of the prefoamed foam beads to the molding and the resulting mechanical properties are improved in particular by coating the expandable thermoplastic polymer particles with a glycerol stearate.
  • the expandable, thermoplastic polymer particles according to the invention can be prefoamed by means of hot air or steam to foam particles having a density in the range of 8 to 200 kg / m 3 , preferably in the range of 10 to 50 kg / m 3 and then welded in a closed mold into foam moldings.
  • Component A Polystyrene PS 158K from BASF SE
  • Component B polyethylene
  • Component D Propellant: pentane S (20% iso-pentane, 80% n-pentane)
  • Nucleating agent talcum (HP 320, Omyacarb)
  • talcum HP 320, omyacarb
  • nucleating agent in the form of a 2.2% by weight polystyrene PS 158 K batch
  • talcum HP 320, omyacarb
  • the melt was extruded through a heated perforated plate (4 holes with 0.65 mm bore and 280 ° C perforated plate temperature).
  • the propellant-containing granules were processed in an EPS prefoamer to foam beads of low density (15-25 g / L prefoamed) and in an EPS molding machine at an overpressure of 0.7 - 1.1 bar to form parts.
  • Example 1 expandable thermoplastic mixtures were prepared with the composition shown in Table 1 in parts by weight. The density and cell number of the foam particles after pre-foaming are summarized in Table 2.
  • the propellant content of the minigranules was determined immediately after preparation and after 7 days storage on filter paper at room temperature and atmospheric pressure by GC analysis.
  • Table 3 shows the deformation residue ⁇ rest of the foam moldings, determined from the single hysteresis at 75% compression (feed 5 mm / min) according to ISO 3386-1.
  • the residual strain ⁇ rest is the percentage after 75% compression, which is missing from the original height of the compressed body.
  • a significant elastification is observed in comparison to pure EPS, which is recognizable by the very high recovery capacity.
  • Example 1 0.3% by weight of a coating composition was drummed onto the surface of the propellant-containing granulate from Example 1 in a Lödige mixer. After a reaction time of 4 hours, the coated, blowing agent-containing granules were prefoamed as in Example 1 and welded into moldings.
  • glycerol tristearate GTS
  • GTS glycerol tristearate
  • GMS glycerol monostearate
  • silica silica
  • the coating agent had a positive effect on the welding of the prefoamed foam beads to the molding.
  • the flexural strength of the moldings obtained according to Example 4 and 5 could be increased to 220 or 227 KPa against 150 kPa of the moldings obtained from the uncoated granules according to Example 1.
  • the melt was extruded at 4 kg / h through a heated perforated plate (4 holes with 0.65 mm bore and 280 ° C orifice plate temperature).
  • the weight proportions of components A to C) are summarized in Table 4.
  • the polymer melt was pressed at 50 kg / h through a tempered to 240-260 ° C perforated plate at 200-220 bar (0.6 mm hole diameter with 7 nests x 7 holes or 0.4 mm Hole diameter with 7 nests x 10 holes).
  • the weight proportions of components A to C) are summarized in Table 4.
  • the propellant-containing granules were processed in an EPS prefoamer to foam beads of low density (15-25 g / L prefoamed) and in an EPS molding machine at an overpressure of 0.7 - 1.1 bar to form parts.
  • Table 4 shows the deformation residue ⁇ rest of the foam moldings, determined from the single hysteresis at 75% compression (feed 5 mm / min) according to ISO 3386-1.
  • the residual strain ⁇ rest is the percentage after 75% compression, which is missing from the original height of the compressed body.
  • a clear elastification is observed in comparison to pure EPS, which is recognizable by the very high recovery capacity.
  • the transmission electron micrograph shows the disperse distribution of the polyethylene in the propellant-containing minigranulate, which after foaming contributes to elastification in the foam.
  • the PE domains of the propellant loaded minigranules are in the order of 200 to 1000 nm.
  • the coating components used were 70% by weight of glycerol tristearate (GTS) and 30% by weight of glycerol monostearate (GMS).
  • GTS glycerol tristearate
  • GMS glycerol monostearate
  • the coating agent had a positive effect on the welding of the prefoamed foam beads to the molding.
  • the flexural strength to 250 or 310 KPa over 150 kPa of the moldings obtained from the uncoated granules are increased.

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Abstract

The invention relates to thermoplastic particle foams having cells with an average cell size in the range of 20 to 500 μm, wherein the cell membranes have a nanocellular or fibrous structure with pore or fiber diameters of less than 1500 nm. The invention also relates to a method for producing said particle foams.

Description

Die Erfindung betrifft thermoplastische Partikelschaumstoffe mit Zellen einer mittleren Zellgröße im Bereich von 20 bis 500 µm, in denen die Zellmembranen eine nanozellulären oder faserförmigen Struktur mit Poren- bzw. Faserdurchmesser unter 1500 nm aufweisen, sowie Verfahren zu ihrer Herstellung.The invention relates to thermoplastic particle foams having cells of average cell size in the range of 20 to 500 microns, in which the cell membranes have a nanocellular or fibrous structure with pore or fiber diameter below 1500 nm, and to processes for their preparation.

Expandierbare Polymermischungen aus Styrolpolymeren, Polyolefinen und gegebenenfalls Lösungsvermittlern, wie hydrierte Styrol-Butadien-Blockcopolymeren, sind beispielsweise aus DE 24 13 375 , DE 24 13 408 oder DE 38 14 783 bekannt. Die daraus erhältlichen Schaumstoffe sollen gegenüber Schaumstoffen aus Styrolpolymeren bessere mechanischen Eigenschaften, insbesondere eine bessere Elastizität und eine geringere Sprödigkeit bei tiefen Temperaturen, sowie eine Unempfindlichkeit gegenüber Lösungsmitteln, wie Essigester und Toluol, aufweisen. Das Treibmittelhaltevermögen und die Verschäumbarkeit der expandierbaren Polymermischungen zu niedrigen Dichten sind für die Verarbeitung jedoch nicht ausreichend.Expandable polymer mixtures of styrene polymers, polyolefins and optionally solubilizers, such as hydrogenated styrene-butadiene block copolymers are, for example DE 24 13 375 . DE 24 13 408 or DE 38 14 783 known. The foams obtainable therefrom are said to have better mechanical properties than foams of styrene polymers, in particular better elasticity and lower brittleness at low temperatures, and insensitivity to solvents such as ethyl acetate and toluene. However, the propellant holding capacity and the foamability of the expandable polymer blends at low densities are not sufficient for processing.

Die WO 2005/056652 beschreibt Partikelschaumstoffformteile mit einer Dichte im Bereich von 10 bis 100 g/l, die durch Verschweißen von vorgeschäumten Schaumpartikeln aus expandierbaren, thermoplastischen Polymergranulaten erhältlich sind. Die Polymergranulate enthalten Mischungen aus Styrolpolymeren und anderen thermoplastischen Polymeren und können durch Schmeizeimprägnierung und anschließender Druckunterwassergranulierung erhalten werden.The WO 2005/056652 describes particle foam moldings having a density in the range of 10 to 100 g / l, which are obtainable by welding prefoamed foam particles of expandable, thermoplastic polymer granules. The polymer granules contain mixtures of styrenic polymers and other thermoplastic polymers and can be obtained by melt impregnation followed by pressurized underwater granulation.

Des Weiteren sind elastische Partikelschaumstoffe aus expandierbaren Interpolymerpartikeln bekannt (z. B. US 2004/0152795 A1 ). Die Interpolymeren sind durch Polymerisation von Styrol in Gegenwart von Polyolefinen in wässriger Suspension erhältlich und bilden ein Interpenetrierendes Netzwerk aus Styropolymeren und Olefinpolymeren. Aus den expandierbaren Polymerpartikeln diffundiert das Treibmittel jedoch schnell heraus, so dass sie bei tiefen Temperaturen gelagert werden müssen und nur eine kurze Zeit eine ausreichende Verschäumbarkeit aufweisen.Furthermore, elastic particle foams made of expandable interpolymer particles are known (eg. US 2004/0152795 A1 ). The interpolymers are obtainable by polymerization of styrene in the presence of polyolefins in aqueous suspension and form an interpenetrating network of styrenopolymers and olefin polymers. From the expandable polymer particles, however, the blowing agent diffuses out quickly, so that they must be stored at low temperatures and only a short time have sufficient foamability.

Die WO 2005/092959 beschreibt nanoporöse Polymerschaumstoffe, die aus treibmittelhaltigen, mehrphasigen Polymermischungen mit Domänen im Bereich von 5 bis 200 nm erhältlich sind. Bevorzugt bestehen die Domänen aus einem durch Emulsionspolymerisation erhältlichen Kern-Schale-Teilchen, in denen die Löslichkeit des Treibmittels mindestens doppelt so hoch ist, als in den angrenzenden Phasen.The WO 2005/092959 describes nanoporous polymer foams obtainable from propellant-containing multiphase polymer blends with domains in the range of 5 to 200 nm. Preferably, the domains consist of a shell-shell particle obtainable by emulsion polymerization in which the solubility of the blowing agent is at least twice as high as in the adjacent phases.

Aufgabe der vorliegenden Erfindung war es, expandierbare, thermoplastische Polymerpartikel mit geringem Treibmittelverlust und hohem Expansionsvermögen bereitzustellen, die zu Partikelschaumstoffen mit hoher Steifigkeit und gleichzeitig guter Elastizität verarbeitbar sind, sowie ein Verfahren zu deren Herstellung.The object of the present invention was to provide expandable, thermoplastic polymer particles with low blowing agent loss and high expansion capacity, which can be processed into particle foams with high rigidity and at the same time good elasticity, and a process for their preparation.

Demgemäß wurden die oben beschriebenen thermoplastischen Partikelschaumstoffe gefunden.Accordingly, the above-described thermoplastic particulate foams have been found.

Die thermoplastischen Partikelschaumstoffe weisen bevorzugt Zellen einer mittleren Zellgröße im Bereich von 50 bis 250 µm und eine nanozelluläre Struktur oder eine faserförmig verstreckte, disperse Phasenstruktur in den Zellwänden der thermoplastischen Partikelschaumstoffe mit einem mittleren Poren- bzw- Faserdurchmesser im Bereich von 10 bis 1000 nm, besonders bevorzugt im Bereich von 100 bis 500 nm auf.The thermoplastic particle foams preferably have cells of average cell size in the range of 50 to 250 microns and a nanocellular structure or a fibrous stretched, disperse phase structure in the cell walls of the thermoplastic particle foams with a mean pore or fiber diameter in the range of 10 to 1000 nm, especially preferably in the range of 100 to 500 nm.

In der transmissionselektronenmikroskopischen Aufnahme (TEM) ist die Zellstruktur mit nanozellulären Zellwänden und Stegen zu erkennen. Figur 1 zeigt einen Schnitt durch die Zellen eines erfindungsgemäßen thermoplastischen Partikelschaumstoffes. Figur 2 zeigt einen 10-fach vergrößerten Ausschnitt aus der in Figur 1 gezeigten Zellstruktur mit einer nanozellulären Zellwand.In the transmission electron micrograph (TEM), the cell structure with nanocellular cell walls and bars can be recognized. FIG. 1 shows a section through the cells of a thermoplastic particle foam according to the invention. FIG. 2 shows a 10x enlarged detail of the in FIG. 1 shown cell structure with a nanocellular cell wall.

Die Polymermatrix der thermoplastischen Partikelschaumstoffe bestehen bevorzugt aus einer kontinuierlichen, Styrolpolymer-reichen Phase und eine dispersen Polyolefin-reichen Phase.The polymer matrix of the thermoplastic particle foams preferably consists of a continuous, styrene polymer-rich phase and a dispersed polyolefin-rich phase.

Besonders bevorzugt enthalten die thermoplastischen Partikelschaumstoffen eine Polymermatrix aus

  1. A) 45 bis 98,9 Gew.-%, insbesondere 55 bis 89,9 Gew.-% eines Styrolpolymeren, insbesondere Polystyrol,
  2. B) 1 bis 45 Gew.-%, insbesondere 4 bis 37 Gew.-% eines Polyolefins, insbesondere Polyethylen und
  3. C) 0,1 bis 10 Gew.-%, insbesondere 3 bis 8 Gew.-% eines hydrierten oder unhydrierten Styrol-Butadien-Blockcopolymeren.
Particularly preferably, the thermoplastic particle foams contain a polymer matrix
  1. A) from 45 to 98.9% by weight, in particular from 55 to 89.9% by weight, of a styrene polymer, in particular polystyrene,
  2. B) 1 to 45 wt .-%, in particular 4 to 37 wt .-% of a polyolefin, in particular polyethylene and
  3. C) 0.1 to 10 wt .-%, in particular 3 to 8 wt .-% of a hydrogenated or unhydrogenated styrene-butadiene block copolymers.

Die erfindungsgemäßen thermoplastischen Partikelschaumstoffe können durch ein Verfahren erhalten werden, bei dem man

  1. a) eine Polymermischungen mit einer kontinuierlichen und einer dispersen Phase durch Mischen zweier unverträglicher thermoplastischer Polymeren und gegebenenfalls einem Verträglichkeitsvermittler herstellt,
  2. b) diese Mischungen mit einem Treibmittel imprägniert und zu expandierbaren thermoplastischen Polymerpartikel granuliert,
  3. c) die expandierbaren, thermoplastischen Polymerpartikel zu Schaumstoffpartikeln vorschäumt, und
  4. d) die vorgeschäumten Schaumstoffpartikel in einer Form mit Heißluft oder Wasserdampf bei einem Verarbeitungsdruck, der so niedrig gewählt wird, dass die nanozelluläre oder faserförmige Struktur in den Zellmembranen erhalten bleibt und üblicherweise im Bereich von 1,5 bis 2,3 bar liegt, zu Partikelschaumstoffformteilen verschweißt.
The thermoplastic particulate foams according to the invention can be obtained by a process in which
  1. a) produces a polymer mixture having a continuous and a disperse phase by mixing two incompatible thermoplastic polymers and optionally a compatibilizer,
  2. b) impregnating these mixtures with a blowing agent and granulating them into expandable thermoplastic polymer particles,
  3. c) prefoaming the expandable, thermoplastic polymer particles into foam particles, and
  4. d) the prefoamed foam particles in a mold with hot air or water vapor at a processing pressure chosen to be so low that the nano-cellular or fibrous structure is retained in the cell membranes and is usually in the range of 1.5 to 2.3 bar, welded to particle foam moldings.

In einer weiteren Ausführungsform kann in Stufe b) die Polymermischung auch zuerst granuliert und die Granulate anschließend in wässriger Phase unter Druck und erhöhter Temperatur mit einem Treibmittel zu expandierbaren thermoplastischen Polymerpartikel nachimprägniert werden. Diese können anschließend nach Abkühlen unter die Schmelzetemperatur der Polymermatrix isoliert oder direkt durch Druckentspannung als vorgeschäumten Schaumstoffpartikeln (Stufe c) erhalten werden.In a further embodiment, in step b) the polymer mixture can also be granulated first and the granules subsequently re-impregnated in the aqueous phase under pressure and elevated temperature with a blowing agent to form expandable thermoplastic polymer particles. These can then be isolated after cooling below the melt temperature of the polymer matrix or obtained directly by pressure release as prefoamed foam particles (stage c).

Es ist aus dem Bereich der mehrphasigen Polymersysteme bekannt, dass die meisten Polymere nicht oder nur geringfügig miteinander mischbar sind (Flory), so dass es je nach Temperatur, Druck und chemischer Zusammensetzung zur Entmischung in jeweilige Phasen kommt. Werden unverträgliche Polymere kovalent miteinander verknüpft, so findet die Entmischung nicht auf makroskopischer, sondern lediglich auf mikroskopischer Ebene statt, d.h. auf der Längenskala der einzelnen Polymerkette. In diesem Fall spricht man daher von Mikrophasenseparation. Daraus resultieren eine Vielzahl von mesoskopischen Strukturen, z.B. lamellare, hexagonale, kubische und bikontinuierliche Morphologien, die eine starke Verwandtschaft mit lyotropen Phasen aufweisen.It is known from the field of multiphase polymer systems that most polymers are immiscible or only slightly miscible with each other (Flory), so that depending on the temperature, pressure and chemical composition for segregation in respective phases. If incompatible polymers are covalently linked together, the segregation does not take place on a macroscopic level, but only on a microscopic level, ie. on the length scale of the individual polymer chain. In this case one speaks therefore of microphase separation. This results in a variety of mesoscopic structures, e.g. lamellar, hexagonal, cubic and bicontinuous morphologies strongly related to lyotropic phases.

Die Polymermischung mit einer kontinuierlichen und einer dispersen Phase kann durch Mischen von zwei unverträglichen thermoplastischen Polymeren, beispielsweise in einem Extruder, hergestellt werden.The polymer mixture having a continuous and a disperse phase can be prepared by mixing two incompatible thermoplastic polymers, for example in an extruder.

Die Polymermischung enthält bevorzugt 45 bis 98,9 Gew.-%, besonders bevorzugt 55 bis 89,9 Gew.-% eines thermoplastischen Polymeren A), insbesondere Styrolpolymeren wie Standard (GPPS)- oder Schlagzähpolystyrol (HIPS) oder Styrol-Acrylnitril-Copolymere (SAN) oder Acrylnitril-Butadien-Styrol-Copolymere (ABS). Besonders bevorzugt werden Standard-Polystyroltypen mit gewichtsmittleren Molekulargewichten im Bereich von 120.000 bis 300.000 g/mol und einer Schmelzevolumenrate MVR (200°C/5 kg) nach ISO 113 im Bereich von 1 bis 10 cm3/10 min, beispielsweise PS 158 K, 168 N oder 148 G der BASF Aktiengesellschaft. Zur Verbesserung der Verschweißung der Schaumstoffpartikel bei der Verarbeitung zum Formteil können leichtfließende Typen, beispielsweise Empera® 156L (Innovene) zugesetzt werdenThe polymer mixture preferably contains 45 to 98.9% by weight, particularly preferably 55 to 89.9% by weight of a thermoplastic polymer A), in particular styrene polymers such as standard (GPPS) or impact polystyrene (HIPS) or styrene-acrylonitrile copolymers (SAN) or acrylonitrile-butadiene-styrene copolymers (ABS). Standard polystyrene types are particularly preferred having weight average molecular weights ranging from 120,000 to 300,000 g / mol and a melt volume rate MVR (200 ° C / 5 kg) according to ISO 113 in the range of 1 to 10 cm 3/10 min, for example PS 158 K, 168 N or 148 G of BASF Aktiengesellschaft. To improve the fusion of the foam particles during processing to the molded part, easily flowing types, for example Empera® 156L (Innovene), can be added

Als weitere Komponente B) enthält die Polymermischung bevorzugt 1 bis 45 Gewichtsprozent, insbesondere 4 bis 37 Gew.-% eines mit dem thermoplastischen Polymeren A) unverträgliches, ebenfalls thermoplastischen Polymeren B). Als Polymer B) wird bevorzugt ein Polyolefin, z. B. Homo- oder Copolymerer von Ethylen und/oder Propylen, insbesondere Polyethylen verwendet, insbesondere wenn als Polymer A) ein Styrolpolymer eingesetzt wird. Als Polypropylene kommen insbesondere Spritzgusstypen, wie Adstif® RA 748 T oder Schlagzähtypen wie Clyrell® EM 2484 der Firma Basell in Betracht. Als Polyethylene kommen kommerziell erhältliche Homopolymere aus Ethylen, wie PE-LD (Spritzgusstypen), -LLD, -HD, oder Copolymere aus Ethylen und Propylen (z. B Moplen® RP220 und Moplen® RP320 der Basell), Ethylen und Okten (Engage®) oder Ethylen und Vinylacetat (EVA), Polyethylenacrylate (EA), wie Surlyn®-Typen 1901 und 2601 von DuPont oder Ethylen-Butylen-Acrylate (EBA) wie Lucofin® 1400 HN, 1400 HM von Lucobit AG in Frage. Der Schmelzevolumenindex MVI (190°C/2,16 kg) der Polyethylene liegt üblicherweise im Bereich von 0,5 bis 40 g/10 min, die Dichte im Bereich von 0,86 bis 0,97 g/cm3, bevorzugt im Bereich von 0,91 bis 0,95 g/cm3. Außerdem können Abmischungen mit Polyisobuten (PIB)(z. B. Oppanol® B150 der BASF Aktengesellschaft) eingesetzt werden.As a further component B), the polymer mixture contains preferably 1 to 45 percent by weight, in particular 4 to 37 wt .-% of an incompatible with the thermoplastic polymer A), also thermoplastic polymer B). As polymer B) is preferably a polyolefin, for. B. homo- or copolymers of ethylene and / or propylene, in particular polyethylene used, in particular when a styrene polymer is used as the polymer A). In particular injection molding grades come as polypropylenes, such as Adstif® RA 748 T or impact types such as Clyrell® EM 2484 from Basell into consideration. Suitable polyethylenes are commercially available homopolymers of ethylene, such as PE-LD (injection molding types), LLD, -HD, or copolymers of ethylene and propylene (for example Moplen® RP220 and Moplen® RP320 from Basell), ethylene and octene (Engage® ) or ethylene and vinyl acetate (EVA), polyethylene acrylates (EA) such as Surlyn® types 1901 and 2601 from DuPont or ethylene-butylene acrylates (EBA) such as Lucofin® 1400 HN, 1400 HM from Lucobit AG. The melt volume index MVI (190 ° C / 2.16 kg) of the polyethylenes is usually in the range of 0.5 to 40 g / 10 min, the density in the range of 0.86 to 0.97 g / cm 3 , preferably in the range from 0.91 to 0.95 g / cm 3 . In addition, blends with polyisobutene (PIB) (eg Oppanol® B150 from BASF Aktengesellschaft) can be used.

Mit geringerem Anteil an Polyolefin nimmt das Treibmittelhaltevermögen deutlich zu. Damit werden die Lagerfähigkeit und die Verarbeitbarkeit der expandierbaren, thermoplastischen Polymerpartikel deutlich verbessert. Im Bereich von 4 bis 20 Gew.-% Polyolefin als Polymer B) erhält man expandierbare thermoplastische Polymerpartikel mit langer Lagerfähigkeit, ohne dass sich die elastischen Eigenschaften des daraus hergestellten Partikelschaumstoffs verschlechtern. Dies zeigt sich beispielsweise in einem geringern Verformungsrest εrest im Bereich von 25 bis 35 %.With a lower proportion of polyolefin, the blowing agent retention capacity increases significantly. Thus, the shelf life and the processability of the expandable thermoplastic polymer particles are significantly improved. In the range from 4 to 20% by weight of polyolefin as polymer B), expandable thermoplastic polymer particles having a long storage life are obtained without the elastic properties of the particle foam produced therefrom deteriorating. This manifests itself, for example, in a lower residual deformation range in the range from 25 to 35%.

Zur gezielten Einstellung der gewünschten Morphologie werden üblicherweise Verträglichkeitsvermittler (Komponente C) in Mengen von 0,1 bis 10 Gew.-%, bevorzugt 3 bis 8 Gew.-%, bezogen auf die Polymermatrix, eingesetzt.For targeted adjustment of the desired morphology are usually compatibilizer (component C) in amounts of 0.1 to 10 wt .-%, preferably 3 to 8 wt .-%, based on the polymer matrix used.

Der Verträglichkeitsvermittler führt zu einer verbesserten Haftung zwischen der Polyolefin-reichen und der Polystyrol-reichen Phase und verbessert die Elastizität des Schaumstoffs schon in geringen Mengen deutlich gegenüber herkömmlichen EPS-Schaumstoffen. Untersuchungen zur Domänengröße der Polyolefin-reichen Phase zeigten, dass der Verträglichkeitsvermittler durch Reduktion der Grenzuflächenspannung kleine Tröpfchen stabilisiert. Die elektronenmikroskopische Aufnahme eines Schnittes durch ein treibmittelhaltiges, expandierbares Polystyrol/Polyethylen zeigt disperse Polyethylendomänen in der Polystyrolmatrix.The compatibilizer leads to improved adhesion between the polyolefin-rich and the polystyrene-rich phase and improves the elasticity of the foam even in small amounts compared to conventional EPS foams. Investigations of the domain size of the polyolefin-rich phase showed that the compatibilizer stabilized small droplets by reducing the interfacial tension. The electron micrograph of a section through a blowing agent-containing, expandable polystyrene / polyethylene shows disperse polyethylene domains in the polystyrene matrix.

Hierfür eignen sich beispielsweise hydrierte oder unhydrierte Styrol-Butadien- oder Styrol-Isopren-Blockcopolymere. Der Gesamtdiengehalt liegt bevorzugt im Bereich von 20 bis 60 Gew.-%, besonders bevorzugt im Bereich von 30 bis 50 Gew.-%, der Gesamtstyrolgehalt liegt entsprechend bevorzugt im Bereich von 40 bis 80 Gew.-%, besonders bevorzugt im Bereich von 50 bis 70 Gew.-%.For example, hydrogenated or unhydrogenated styrene-butadiene or styrene-isoprene block copolymers are suitable for this purpose. The total diene content is preferably in the range from 20 to 60% by weight, particularly preferably in the range from 30 to 50% by weight, the total styrene content is correspondingly preferably in the range from 40 to 80% by weight, particularly preferably in the region of 50 to 70% by weight.

Geeignete Styrol-Butadien-Blockcopolymere, welche aus mindestens zwei Polystyrolblöcken S und mindestens einem Styrol-Butadien-Copolymer-Block S/B bestehen, sind beispielsweise sternförmig verzweigte Blockcopolymere, wie sie in EP-A 0654488 beschrieben sind.Suitable styrene-butadiene block copolymers, which consist of at least two polystyrene blocks S and at least one styrene-butadiene copolymer block S / B, are, for example, star-branched block copolymers, such as those in EP-A 0654488 are described.

Des Weiteren eignen sich Blockcopolymere mit mindestens zwei Hartblöcken S1 und S2 aus vinylaromatischen Monomeren mit mindestens einem dazwischen liegenden statistischen Weichblock B/S aus vinylaromatischen Monomeren und Dien, wobei der Anteil der Hartblöcke über 40 Gew.-%, bezogen auf das gesamte Blockcopolymer beträgt und der 1,2-Vinylgehalt im Weichblock B/S unter 20 % beträgt, wie sie in WO 00/58380 beschrieben sind.Furthermore, block copolymers having at least two hard blocks S 1 and S 2 of vinylaromatic monomers having at least one intermediate random soft block B / S of vinylaromatic monomers and diene are suitable, the proportion of hard blocks being more than 40% by weight, based on the total block copolymer and the 1,2-vinyl content in soft block B / S is below 20%, as in WO 00/58380 are described.

Als Verträglichkeitsvermittler sind auch lineare Styrol-Butadien-Blockcopolymere der allgemeinen Struktur S-(S/B)-S mit ein oder mehreren, zwischen den beiden S-Blöcken liegenden, eine statische Styrol/Butadien-Verteilung aufweisenden Blöcken (S/B)random, geeignet. Solche Blockcopolymeren sind durch anionische Polymerisation in einem unpolaren Lösungsmittel unter Zusatz eines polaren Cosolvens oder eines Kaliumsalzes erhältlich, wie beispielsweise in WO 95/35335 bzw. WO 97140079 beschrieben.Suitable compatibilizers are linear styrene-butadiene block copolymers of the general structure S- (S / B) -S lying with one or more, between the two S blocks, a random styrene / butadiene distribution having blocks (S / B) random , suitable. Such block copolymers are obtainable by anionic polymerization in a non-polar solvent with the addition of a polar cosolvent or a potassium salt, such as in WO 95/35335 respectively. WO 97140079 described.

Als Vinylgehalt wird der relative Anteil an 1,2-Verknüpfungen der Dieneinheiten, bezogen auf die Summe der 1,2-, 1,4-cis und 1,4-trans-Verknüpfungen verstanden. Der 1,2-Vinylgehalt im Styrol-Butadien-Copolymerblock (S/B) liegt bevorzugt unter 20 %, insbesondere im Bereich von 10 bis 18%, besonders bevorzugt im Bereich von 12 bis 16 %.The vinyl content is understood to mean the relative proportion of 1,2-linkages of the diene units, based on the sum of the 1,2-, 1,4-cis and 1,4-trans linkages. The 1,2-vinyl content in the styrene-butadiene copolymer block (S / B) is preferably below 20%, in particular in the range from 10 to 18%, particularly preferably in the range from 12 to 16%.

Als Verträglichkeitsvermittler werden bevorzugt Styrol-Butadien-Styrol (SBS) Dreiblockcopolymere mit einem Butadiengehalt von 20 bis 60 Gew.-%, bevorzugt 30 bis 50 Gew.-%, welche hydriert oder nicht hydriert sein können, verwendet. Diese sind beispielsweise unter der Bezeichnung Styroflex® 2G66, Styrolux® 3G55, Styroclear® GH62, Kraton® D 1101, Kraton® G 1650, Kraton® D 1155, Tuftec® H1043 oder Europren® SOL 6414 im Handel. Dabei handelt es sich um SBS-Blockcopolymere mit scharfen Übergängen zwischen B- und S-Blöcken. Eine Verbesserung der Verträglichkeit kann zusätzlich durch Hydrieren der Butadienblöcke erreicht werden, z. B. Kraton® G Typen.Preferred compatibilizers are styrene-butadiene-styrene (SBS) triblock copolymers having a butadiene content of from 20 to 60% by weight, preferably from 30 to 50% by weight, which may be hydrogenated or unhydrogenated. These are for example under the name Styroflex® 2G66, Styrolux® 3G55, Styroclear® GH62, Kraton® D 1101, Kraton® G 1650, Kraton® D 1155, Tuftec® H1043 or Europren® SOL 6414 commercially. These are SBS block copolymers with sharp transitions between B and S blocks. An improvement in compatibility can be achieved additionally by hydrogenating the butadiene blocks, for. B. Kraton® G types.

Des weiteren können der mehrphasigen Polymermischung Additive, Keimbildner, Weichmacher, Flammschutzmittel, lösliche und unlösliche anorganische und/oder organische Farbstoffe und Pigmente, Füllstoffe oder Cotreibmittel in Mengen zugesetzt werden, die die Domänenbildung und daraus resultierende Schaumstoffstruktur nicht beeinträchtigen.Furthermore, additives, nucleating agents, plasticizers, flameproofing agents, soluble and insoluble inorganic and / or organic dyes and pigments, fillers or co-blowing agents may be added to the multiphase polymer mixture in amounts that do not interfere with the domain formation and resulting foam structure.

Als Keimbildner oder Nukleierungsmittel können beispielsweise Polyolefinwachse oder Talkum zusätzlich in Mengen von 0 bis 5, bevorzugt 0,5 bis 3 Gew.-%, bezogen auf die Polymeren A) bis C) gegeben werden.As nucleating agent or nucleating agent, for example, polyolefin waxes or talc may additionally be added in amounts of 0 to 5, preferably 0.5 to 3 wt .-%, based on the polymers A) to C).

Als Treibmittel (Komponente D) wird in Stufe b) bevorzugt 1 bis 15 Gewichtsprozent, bevorzugt 3 bis 10 Gewichtsprozent, bezogen auf die Polymermischung A) bis C), eines physikalischen Treibmittels, wie aliphatischen C3 bis C8-Kohlenwasserstoffen, Alkoholen, Ketonen, Ethern oder halogenierten Kohlenwasserstoffen eingesetzt. Bevorzugt wird iso-Butan, n-Butan, iso-Pentan, n-Pentan oder iso-Hexan eingesetzt.As blowing agent (component D) in step b) preferably 1 to 15 weight percent, preferably 3 to 10 weight percent, based on the polymer mixture A) to C) of a physical blowing agent, such as aliphatic C 3 to C 8 hydrocarbons, alcohols, ketones , Ethers or halogenated hydrocarbons used. Preference is given to using isobutane, n-butane, isopentane, n-pentane or isohexane.

Geeignete Cotreibmittel sind solche mit einer geringeren Selektivität der Löslichkeit für die Domänen bildenden Phase, beispielsweise Gase wie CO2, N2, Fluorkohlenwasserstoffe oder Edelgase. Diese werden bevorzugt in Mengen von 0 bis 10 Gew.-%, bezogen auf die Polymermischung, eingesetzt.Suitable co-propellants are those having a lower selectivity of solubility for the domain-forming phase, for example, gases such as CO 2 , N 2 , fluorocarbons or noble gases. These are preferably used in amounts of from 0 to 10% by weight, based on the polymer mixture.

Besonders bevorzugt wird ein kontinuierliches Verfahren, bei dem die Stufe a) ein thermoplastisches, die kontinuierliche Phase bildenden Polymer A), beispielsweise Polystyrol, in einem Zweiwellen-Extruder aufgeschmolzen und zur Bildung der Polymermischung mit einem die disperse Phase bildenden Polymer B) und gegebenenfalls Verträglichkeitsvermittler C) vermischt wird und anschließend die Polymerschmelze in Stufe b) durch eine oder mehrere statische und/oder dynamischen Mischelemente gefördert und mit dem Treibmittel imprägniert wird. Die treibmittelbeladene Schmelze kann anschließend durch eine entsprechende Düse zu Schaumstoffplatten, -strängen oder -Partikeln extrudiert und geschnitten werden.Particular preference is given to a continuous process in which stage a) a thermoplastic, the continuous phase forming polymer A), for example polystyrene, melted in a twin-screw extruder and to form the polymer mixture with the disperse phase-forming polymer B) and optionally compatibilizer C) is mixed and then the polymer melt in stage b) by one or more static and / or dynamic mixing elements promoted and impregnated with the blowing agent. The propellant loaded melt may then be extruded through a corresponding die into foam sheets, strands or particles and cut.

Mittels Unterwassergranulierung (UWG) kann die aus der Düse austretende Schmelze auch direkt zu expandierbaren oder gezielt angeschäumten Polymerpartikeln geschnitten werden. Die Einstellung des geeigneten Gegendrucks und einer geeigneten Temperatur im Wasserbad des UWG ermöglicht somit eine gezielte Herstellung von Schaumstoffpartikeln zu ermöglichen.By means of underwater granulation (UWG), the melt emerging from the nozzle can also be cut directly into expandable or selectively foamed polymer particles. The setting of the appropriate backpressure and a suitable temperature in the water bath of the UWG thus allows a targeted production of foam particles to allow.

Zur Herstellung der expandierbaren Polymerpartikel wird die Unterwassergranulierung in der Regel bei Drücken im Bereich von 1,5 bis 10 bar durchgeführt. Die Düsenplatte weist in der Regel mehrere Nester mit mehreren Löchern auf. Bei einem Lochdurchmesser im Bereich von 0,2 bis 1 mm erhält man expandierbare Polymerpartikel mit der bevorzugten mittleren Partikeldurchmesser im Bereich von 0,5 bis 1,5 mm.0,8 mm. Expandierbare Polymerpartikel mit enger Partikelgrößenverteilung und einem mittleren Partikeldurchmesser im Bereich von 0,6 bis 0,8 mm führen zu einer besseren Ausfüllung des Formteilautomaten mit filigranere Formteilgestaltung. Des Weiteren wird dadurch eine bessere Formteiloberfläche erreicht mit weniger Zwickelvolumen.In order to produce the expandable polymer particles, underwater granulation is generally carried out at pressures in the range from 1.5 to 10 bar. The nozzle plate usually has several nests with several holes. With a hole diameter in the range of 0.2 to 1 mm, expandable polymer particles having the preferred mean particle diameter in the range of 0.5 to 1.5 mm.0.8 mm are obtained. Expandable polymer particles with narrow particle size distribution and an average particle diameter in the range of 0.6 to 0.8 mm lead to a better filling of the molding machine with filigree molding design. Furthermore, this achieves a better molding surface with less gusset volume.

Bevorzugt werden die erhaltenen runden oder ovalen Partikel auf einen Durchmesser im Bereich von 0,2 bis 10 mm aufgeschäumt. Ihre Schüttdichte liegt vorzugsweise im Bereich von 10 bis 100 g/l.Preferably, the resulting round or oval particles are foamed to a diameter in the range of 0.2 to 10 mm. Its bulk density is preferably in the range of 10 to 100 g / l.

Der mittlere Durchmesser der dispersen Phase der in Stufe a) hergestellten Polymermischung liegt bevorzugt im Bereich von 1 bis 2000 nm, besonders bevorzugt im Bereich von 100 bis 1500 nm.The average diameter of the disperse phase of the polymer mixture prepared in step a) is preferably in the range from 1 to 2000 nm, particularly preferably in the range from 100 to 1500 nm.

Eine bevorzugte Polymermischungen in Stufe a) wird durch Mischen von

  1. A) 45 bis 98,9 Gewichtsprozent, insbesondere 55 bis 89,9 Gew.-% eines Styrolpolymeren, insbesondere Polystyrol,
  2. B) 1 bis 45 Gewichtsprozent, insbesondere 4 bis 37 Gew.-% eines Polyolefins, insbesondere Polyethylen und
  3. C) 0,1 bis 10 Gewichtsprozent, insbesondere 3 bis 8 Gew.-% eines hydrierten oder unhydrierten Styrol-Butadien-Blockcopolymeren hergestellt.
A preferred polymer blend in step a) is prepared by mixing
  1. A) from 45 to 98.9% by weight, in particular from 55 to 89.9% by weight, of a styrene polymer, in particular polystyrene,
  2. B) 1 to 45 weight percent, in particular 4 to 37 wt .-% of a polyolefin, in particular polyethylene and
  3. C) 0.1 to 10 weight percent, in particular 3 to 8 wt .-% of a hydrogenated or unhydrogenated styrene-butadiene block copolymers produced.

Gegenstand der Erfindung sind auch die in Stufe b) als Zwischenprodukte erhältlichen expandierbaren, thermoplastischen Polymerpartikel, die eine Polymermatrix enthalten aus

  1. A) 45 bis 98,9 Gewichtsprozent, insbesondere 55 bis 89,9Gew.-% eines Styrolpolymeren, insbesondere Polystyrol,
  2. B) 1 bis 45 Gewichtsprozent, insbesondere 4 bis 37 Gew.-% eines Polyolefins, insbeondere Polyethylen und
  3. C) 0,1 bis 10 Gewichtsprozent, insbesondere 1 bis 8 Gew.-% eines hydrierten oder unhydrierten Styrol-Butadien-Blockcopolymeren, wobei die Summe aus A) bis C) 100 Gew.-% ergibt, und zusätzlich
  4. D) 1 bis 15 Gewichtsprozent, insbesondere 3 bis 10 Gew.-%, bezogen auf die Polymermatrix, eines Treibmittels,
  5. E) 0 bis 5, vorzugsweise 0,3 bis 3 Gew.-% eines Nukleierungsmittels.
The invention also provides the expandable, thermoplastic polymer particles which are obtainable as intermediates in step b) and which comprise a polymer matrix
  1. A) from 45 to 98.9% by weight, in particular from 55 to 89.9% by weight, of a styrene polymer, in particular polystyrene,
  2. B) 1 to 45 weight percent, in particular 4 to 37 wt .-% of a polyolefin, in particular polyethylene and
  3. C) 0.1 to 10 weight percent, in particular 1 to 8 wt .-% of a hydrogenated or unhydrogenated styrene-butadiene block copolymer, wherein the sum of A) to C) 100 wt .-% results, and in addition
  4. D) 1 to 15% by weight, in particular 3 to 10% by weight, based on the polymer matrix, of a blowing agent,
  5. E) 0 to 5, preferably 0.3 to 3 wt .-% of a nucleating agent.

Zur Verbesserung der Verarbeitbarkeit können die fertigen expandierbaren thermoplastischen Polymerpartikel durch Glycerinester, Antistatika oder Antiverklebungsmittel beschichtet werden.To improve processability, the final expandable thermoplastic polymer particles may be coated by glycerol esters, antistatic agents or anticaking agents.

Die Verschweißung der vorgeschäumten Schaumstoffperlen zum Formteil und die daraus resultierenden mechanischen Eigenschaften werden insbesondere durch Beschichtung der expandierbaren thermoplastischen Polymerpartikel mit einem Glycerinstearat verbessert. Besonders bevorzugt wird eine Beschichtung aus 50 bis 100 Gew.-% Glycerintristearat (GTS), 0 bis 50 Gew.-% Glycerinmonostearat (GMS) und 0 bis 20 Gew.-% Kieselsäure verwendet.The welding of the prefoamed foam beads to the molding and the resulting mechanical properties are improved in particular by coating the expandable thermoplastic polymer particles with a glycerol stearate. Particularly preferred is a coating of 50 to 100 wt .-% glyceryl tristearate (GTS), 0 to 50 wt .-% glycerol monostearate (GMS) and 0 to 20 wt .-% silica used.

Die erfindungsgemäßen expandierbaren, thermoplastischen Polymerpartikel können mittels Heißluft oder Wasserdampf zu Schaumpartikeln mit einer Dichte im Bereich von 8 bis 200 kg/m3, bevorzugt im Bereich von 10 bis 50 kg/m3 vorgeschäumt und anschließend in einer geschlossenen Form zu Schaumstoffformkörpern verschweißt werden.The expandable, thermoplastic polymer particles according to the invention can be prefoamed by means of hot air or steam to foam particles having a density in the range of 8 to 200 kg / m 3 , preferably in the range of 10 to 50 kg / m 3 and then welded in a closed mold into foam moldings.

BeispieleExamples Einsatzstoffe:Starting Materials: Komponente A: Polystyrol PS 158K der BASF SEComponent A: Polystyrene PS 158K from BASF SE Komponente B: PolyethylenComponent B: polyethylene

  • B1: PE-LLD (LL1201 XV, Exxon Mobile, Dichte 0,925 g/L, MVI = 0,7 g/10 min, Schmelzpunkt 123°C)B1: LLDPE (LL1201 XV, Exxon Mobile, density 0.925 g / L, MVI = 0.7 g / 10 min, melting point 123 ° C)
  • B2: PE-LLD (LL1001 XV, Exxon Mobile, Dichte 0,918 g/L, MVI = 1,0 g/10 min, Schmelzpunkt 120°C))B2: LLDPE (LL1001 XV, Exxon Mobile, density 0.918 g / L, MVI = 1.0 g / 10 min, melting point 120 ° C))
Komponente C:Component C:

  • C: Styrolux® 3G55, Styrol-Butadien-Blockcopolymer der BASF SE,C: Styrolux® 3G55, styrene-butadiene block copolymer from BASF SE,
Komponente D: Treibmittel: Pentan S (20% iso-Pentan, 80% n-Pentan)Component D: Propellant: pentane S (20% iso-pentane, 80% n-pentane) Nukleierungsmittel: Talkum (HP 320, Omyacarb)Nucleating agent: talcum (HP 320, Omyacarb) Beispiel 1example 1

In einem Zweischneckenextruder der Firma Leitritz ZSK 18 wurden 22 Gew. % PE-LLD (LL1201 XV, Exxon Mobile) mit 69,6 Gew. % Polystyrol (PS 158K, BASF) und 4 Gew. % SBS-Blockcopolymer (Styrolux® 3G55, BASF) bei 220-240°C aufgeschmolzen. Anschließend wurde die Polymerschmelze mit 8 Gew. % s-Pentan, bezogen auf die Polymermatrix, beladen. Danach wurde die Polymerschmelze in zwei statischen Mischern homogenisiert und auf 180°C abgekühlt. Zu dem treibmittelbeladenen Hauptschmelzestrom wurde über einen Seitenextruder 2,2 Gew. % Talkum (HP 320, Omyacarb), bezogen auf die Polymermatrix, als Nukleierungsmittel in Form eines Batches mit 2,2 Gew.-% Polystyrol PS 158 K zugegeben. Nach Homogenisierung über zwei weitere statische Mischer wurde die Schmelze durch eine beheizte Lochplatte extrudiert (4 Löcher mit 0,65 mm Bohrung und 280°C Lochplattentemperatur). Der Polymerstrang wurde mittels Unterwassergranulierung abgeschlagen (12 bar Unterwasserdruck, 45°C Wassertemperatur), so dass ein treibmittelbeladenes Minigranulat mit enger Teilchengrößenverteilung (d'= 1,2 mm) erhalten wurde.In a twin-screw extruder Leitritz ZSK 18 22 wt.% PE-LLD (LL1201 XV, Exxon Mobile) with 69.6 wt.% Polystyrene (PS 158K, BASF) and 4 wt.% SBS block copolymer (Styrolux® 3G55, BASF) melted at 220-240 ° C. Subsequently, the polymer melt was loaded with 8% by weight of s-pentane, based on the polymer matrix. Thereafter, the polymer melt was homogenized in two static mixers and cooled to 180 ° C. 2.2% by weight of talcum (HP 320, omyacarb), based on the polymer matrix, as nucleating agent in the form of a 2.2% by weight polystyrene PS 158 K batch was added to the blowing agent-laden main melt stream via a side extruder. After homogenization via two further static mixers, the melt was extruded through a heated perforated plate (4 holes with 0.65 mm bore and 280 ° C perforated plate temperature). The polymer strand was beaten off by means of underwater granulation (12 bar underwater pressure, 45 ° C. water temperature), so that a propellant-loaded minigranulate having a narrow particle size distribution (d '= 1.2 mm) was obtained.

Das treibmittelhaltige Granulat wurde in einem EPS-Vorschäumer zu Schaumperlen geringer Dichte (15-25 g/L vorgeschäumt) und in einem EPS-Formteilautomaten bei einem Überdruck von 0,7 - 1,1 bar zu Formteilen verarbeitet.The propellant-containing granules were processed in an EPS prefoamer to foam beads of low density (15-25 g / L prefoamed) and in an EPS molding machine at an overpressure of 0.7 - 1.1 bar to form parts.

Beispiele 2 und 3 und VergleichsversuchExamples 2 and 3 and comparative experiment

Analog Beispiel 1 wurden expandierbare Thermoplastmischungen mit der in Tabelle 1 angegebenen Zusammensetzung in Gewichtsanteilen hergestellt. Die Dichte und Zellzahl der Schaumstoffpartikel nach dem vorschäumen sind in Tabelle 2 zusammengestellt.As in Example 1 expandable thermoplastic mixtures were prepared with the composition shown in Table 1 in parts by weight. The density and cell number of the foam particles after pre-foaming are summarized in Table 2.

Der Treibmittelgehalt des Minigranulats (Gew.-%) wurde sofort nach der Herstellung und nach 7 Tagen Lagerung auf Filterpapier bei Raumtemperatur und Atmosphärendruck mittels GC-Analyse bestimmt.The propellant content of the minigranules (% by weight) was determined immediately after preparation and after 7 days storage on filter paper at room temperature and atmospheric pressure by GC analysis.

An den Formteilen wurden verschiedene mechanische Messungen durchgeführt um die Elastifizierung des Schaumstoffs nachzuweisen. Tabelle 3 zeigt den Verformungsrest εrest der Schaumstoffformteile, ermittelt aus der Einfachhysterese bei 75% Stauchung (Vorschub 5mm/min) nach ISO 3386-1. Der Verformungsrest εrest ist der prozentuale Anteil nach 75% Stauchung, der zur Ursprungshöhe des gestauchten Körpers fehlt. Bei den erfindungsgemäßen Beispielen wird im Vergleich zum reinen EPS eine deutliche Elastifizierung beobachtet, die an dem sehr hohen Rückstellungsvermögen erkennbar ist.Various mechanical measurements were carried out on the molded parts in order to demonstrate the elasticity of the foam. Table 3 shows the deformation residue ε rest of the foam moldings, determined from the single hysteresis at 75% compression (feed 5 mm / min) according to ISO 3386-1. The residual strain ε rest is the percentage after 75% compression, which is missing from the original height of the compressed body. In the examples according to the invention a significant elastification is observed in comparison to pure EPS, which is recognizable by the very high recovery capacity.

In der transmissionselektronenmikroskopischen Aufnahme (TEM) ist die Zellstruktur (Figur 1) mit nanozellulären Zellwänden und Stegen (Figur 2) zu erkennen, die zu der Elastifizierung beitragen. Die Poren liegen dabei in der Größenordnung von 200 bis 500 nm und entsprechen der PE-Domänen des treibmittelbeladenen Minigranulats. Tabelle 1: Zusammensetzung der expandierbaren Thermoplastmischungen (Gewichtsanteile) V Beisp.1 Beisp. 2 Beisp. 3 PS 158K 97,8 71,8 59,8 46,8 PE 22 33 44 3G55 4 6 8 Talkum 2,2 2,2 2,2 2,2 Treibmittelgehalt (s-Pentan) 6,8 6,5 6,5 8,2 Treibmittelgehalt (s-Pentan) nach 7 Tagen 5,7 4,8 4 3 Tabelle 2: Eigenschaften der Schaumstoffpartikel V Beisp.1 Beisp. 2 Beisp. 3 Dichte [kg/m3] 18 18 23 26 Zellzahl [1/mm] 11,6 4,5 6,0 6,8 Tabelle 3: Verformungsrest εrest der Schaumstoffformteile bei 75% Stauchung Verarbeitungsdruck V Beisp.1 Beisp. 2 Beisp. 3 0,8 bar 60 23 32 0,9 bar 59 26 33 1,0 bar 58 28 49 1,1 bar 60 60 55 55 In the transmission electron micrograph (TEM), the cell structure ( FIG. 1 ) with nanocellular cell walls and bridges ( FIG. 2 ), which contribute to elastification. The pores are on the order of 200 to 500 nm and correspond to the PE domains of the propellant loaded minigranules. Table 1: Composition of the expandable thermoplastic mixtures (parts by weight) V Beisp.1 Ex. 2 Ex. 3 PS 158K 97.8 71.8 59.8 46.8 PE 22 33 44 3G55 4 6 8th talc 2.2 2.2 2.2 2.2 Blowing agent content (s-pentane) 6.8 6.5 6.5 8.2 Propellant content (s-pentane) after 7 days 5.7 4.8 4 3 V Beisp.1 Ex. 2 Ex. 3 Density [kg / m 3 ] 18 18 23 26 Cell number [1 / mm] 11.6 4.5 6.0 6.8 processing pressure V Beisp.1 Ex. 2 Ex. 3 0.8 bar 60 23 32 0.9 bar 59 26 33 1.0 bar 58 28 49 1.1 bar 60 60 55 55

Beispiele 4 und 5Examples 4 and 5

Zur Verbesserung der Verschweißung der Schaumstoffpartikel, wurde auf die Oberfläche des treibmittelhaltigen Granulates aus Beispiel 1 in einem Lödige-Mischer 0,3 Gew. % eines Beschichtungsmittels aufgetrommelt. Nach einer Einwirkzeit von 4 Stunden wurde das beschichtete, treibmittelhaltige Granulat wie in Beispiel 1 vorgeschäumt und zu Formteilen verschweißt.To improve the welding of the foam particles, 0.3% by weight of a coating composition was drummed onto the surface of the propellant-containing granulate from Example 1 in a Lödige mixer. After a reaction time of 4 hours, the coated, blowing agent-containing granules were prefoamed as in Example 1 and welded into moldings.

Als Beschichtungskomponenten wurden für Beispiel 4 Glycerintristearat (GTS) und für Beispiel 5 eine Mischung aus 60 Gew.-% GTS, 30 Gew.-% Glycerinmonostearat (GMS) und 10 Gew.-% Kieselsäure verwendet. Das Beschichtungsmittel hatte einen positiven Effekt auf die Verschweißung der vorgeschäumten Schaumstoffperlen zum Formteil. Die Biegefestigkeit der nach Beispiel 4 und 5 erhaltenen Formteile konnte auf 220 bzw. 227 KPa gegenüber 150 kPa der aus den unbeschichteten Granulaten nach Beispiel 1 erhaltenen Formteile, erhöht werden.As coating components, for example 4, glycerol tristearate (GTS) and for example 5 a mixture of 60% by weight GTS, 30% by weight glycerol monostearate (GMS) and 10% by weight silica were used. The coating agent had a positive effect on the welding of the prefoamed foam beads to the molding. The flexural strength of the moldings obtained according to Example 4 and 5 could be increased to 220 or 227 KPa against 150 kPa of the moldings obtained from the uncoated granules according to Example 1.

Beispiele 6 bis 12Examples 6 to 12

In einem Zweischneckenextruder der Firma Leitritz ZSK 18 wurden die Komponenten A bis C bei 220-240°C / 130 bar aufgeschmolzen. Anschließend wurde in die Polymerschmelze 8 Gewichtsanteile Pentan S (20% iso-Pentan, 80% n-Pentan) als Treibmittel gedrückt und über zwei statische Mischer homogen in die Polymerschmelze eingearbeitet. Danach wurde über einen Kühler die Temperatur auf 180° - 185°C reduziert. Zu dem treibmittelbeladenen Hauptschmelzestrom wurde über einen Seitenextruder 2,2 Gewichtsanteile Talkum (HP 320, Omyacarb) als Nukleierungsmittel in Form eines 50 Gew.-%igen Polystyrol-Batches zudosiert. Nach Homogenisierung über zwei weitere statische Mischer wurde die Schmelze mit 4 kg/h durch eine beheizte Lochplatte extrudiert (4 Löcher mit 0,65 mm Bohrung und 280°C Lochplattentemperatur). Der Polymerstrang wurde mittels Unterwassergranulierung abgeschlagen (12 bar Unterwasserdruck, 45°C Wassertemperatur), so dass ein treibmittelbeladenes Minigranulat mit enger Teilchengrößenverteilung (d'= 1,1 mm) erhalten wurde. Die Gewichtsanteile der Komponenten A bis C) sind in Tabelle 4 zusammengestellt.In a twin-screw extruder Leitritz ZSK 18, the components A to C were melted at 220-240 ° C / 130 bar. Subsequently, 8 parts by weight of pentane S (20% isopentane, 80% n-pentane) as blowing agent were pressed into the polymer melt and incorporated homogeneously into the polymer melt via two static mixers. Thereafter, the temperature was reduced to 180 ° - 185 ° C via a condenser. 2.2 parts by weight of talcum (HP 320, omyacarb) as nucleating agent in the form of a 50% by weight polystyrene batch were added via a side extruder to the blowing agent-laden main melt stream. After homogenization via two further static mixers, the melt was extruded at 4 kg / h through a heated perforated plate (4 holes with 0.65 mm bore and 280 ° C orifice plate temperature). The polymer strand was beaten off by means of underwater granulation (12 bar underwater pressure, 45 ° C. water temperature), so that a propellant-loaded minigranulate having a narrow particle size distribution (d '= 1.1 mm) was obtained. The weight proportions of components A to C) are summarized in Table 4.

Beispiele 13:Examples 13:

In einem Zweischneckenextruder der Firma Leitritz ZE 40 wurden die Komponenten A bis C bei 240 - 260°C / 140 bar aufgeschmolzen und mit 2,2 Gewichtsanteilen Talkum (HP 320, Omyacarb) als Nukleierungsmittel versetzt. Anschließend wurde in die Polymermelze mit 8 Gewichtsanteilen Pentan S (20% iso-Pentan, 80% n-Pentan) als Treibmittel gedrückt und über zwei statische Mischer homogen in die Polymerschmelze eingearbeitet. Danach wurde über einen Kühler die Temperatur auf 180°-195°C reduziert. Nach weiterer Homogenisierung über zwei weitere statische Mischer, wurde die Polymerschmelze mit 50 kg/h durch eine auf 240 - 260°C temperierte Lochplatte bei 200 - 220 bar gedrückt (0,6 mm Lochdurchmesser mit 7 Nester x 7 Löcher oder 0,4 mm Lochdurchmesser mit 7 Nester x 10 Löcher). Der Polymerstrang wurde mittels Unterwassergranulierung abgeschlagen (11-10 bar Unterwasserdruck bei 40°C-50°C Wassertemperatur), so dass ein treibmittelbeladenes Minigranulat mit enger Teilchengrößenverteilung (d'= 1,1 mm bei 0,6 mm Lochdurchmesser und 0,8 mm bei 0,4 mm Lochdurchmesser) erhalten wurde. Die Gewichtsanteile der Komponenten A bis C) sind in Tabelle 4 zusammengestellt.In a twin-screw extruder Leitritz ZE 40, the components A to C at 240 - 260 ° C / 140 bar were melted and treated with 2.2 parts by weight of talc (HP 320, omyacarb) as a nucleating agent. Subsequently, pentane S (20% isopentane, 80% n-pentane) as blowing agent was pressed into the polymer melt with 8 parts by weight and incorporated homogeneously into the polymer melt via two static mixers. Thereafter, the temperature was reduced to 180 ° -195 ° C via a condenser. After further homogenization via two further static mixers, the polymer melt was pressed at 50 kg / h through a tempered to 240-260 ° C perforated plate at 200-220 bar (0.6 mm hole diameter with 7 nests x 7 holes or 0.4 mm Hole diameter with 7 nests x 10 holes). The polymer strand was beaten off by means of underwater granulation (11-10 bar underwater pressure at 40 ° C.-50 ° C. water temperature), so that a propellant-laden minigranulate having a narrow particle size distribution (d '= 1.1 mm at 0.6 mm hole diameter and 0.8 mm at 0.4 mm hole diameter). The weight proportions of components A to C) are summarized in Table 4.

Das treibmittelhaltige Granulat wurde in einem EPS-Vorschäumer zu Schaumstoffperlen geringer Dichte (15-25 g/L vorgeschäumt) und in einem EPS-Formteilautomaten bei einem Überdruck von 0,7 - 1,1 bar zu Formteilen verarbeitet.The propellant-containing granules were processed in an EPS prefoamer to foam beads of low density (15-25 g / L prefoamed) and in an EPS molding machine at an overpressure of 0.7 - 1.1 bar to form parts.

An den Formteilen wurden verschiedene mechanische Messungen durchgeführt um die Elastifizierung des Schaumstoffs nachzuweisen. Tabelle 4 zeigt den Verformungsrest εrest der Schaumstoffformteile, ermittelt aus der Einfachhysterese bei 75% Stauchung (Vorschub 5mm/min) nach ISO 3386-1. Der Verformungsrest εrest ist der prozentuale Anteil nach 75% Stauchung, der zur Ursprungshöhe des gestauchten Körpers fehlt. Bei den erfindungsgemäßen Beispielen wird im Vergleich zum reinen EPS eine deutliche Elastifizierung beobachtet, die an dem sehr hohen Rückstellungvermögen erkennbar ist.Various mechanical measurements were carried out on the molded parts in order to demonstrate the elasticity of the foam. Table 4 shows the deformation residue ε rest of the foam moldings, determined from the single hysteresis at 75% compression (feed 5 mm / min) according to ISO 3386-1. The residual strain ε rest is the percentage after 75% compression, which is missing from the original height of the compressed body. In the examples according to the invention a clear elastification is observed in comparison to pure EPS, which is recognizable by the very high recovery capacity.

In der transmissionselektronenmikroskopischen Aufnahme (TEM) ist die disperse Verteilung des Polyethylens im treibmittelhaltigen Minigranulat zu erkennen, die nach dem Verschäumen zur Elastifizierung im Schaumstoff beitragen. Die PE-Domänen des des treibmittelbeladenen Minigranulats liegen dabei in der Größenordnung von 200 bis 1000 nm.The transmission electron micrograph (TEM) shows the disperse distribution of the polyethylene in the propellant-containing minigranulate, which after foaming contributes to elastification in the foam. The PE domains of the propellant loaded minigranules are in the order of 200 to 1000 nm.

Als Beschichtungskomponenten wurde 70 Gew.-% Gycerintristearat (GTS) und 30 Gew.-% Glycerinmonostearat (GMS) verwendet. Das Beschichtungsmittel hatte einen positiven Effekt auf die Verschweißung der vorgeschäumten Schaumstoffperlen zum Formteil. Die Biegefestigkeit auf 250 bzw. 310 KPa gegenüber 150 kPa der aus den unbeschichteten Granulaten erhaltenen Formteile, erhöht werden.The coating components used were 70% by weight of glycerol tristearate (GTS) and 30% by weight of glycerol monostearate (GMS). The coating agent had a positive effect on the welding of the prefoamed foam beads to the molding. The flexural strength to 250 or 310 KPa over 150 kPa of the moldings obtained from the uncoated granules are increased.

Die kleinen Partikelgrößen 0,8 mm zeigten eine Verbesserung bei der Verarbeitbarkeit zum Formteil bezüglich Entformzeiten und Füllverhalten des Werkzeugs. Zusätzlich wurde die Formteiloberfläche homogener als bei Partikeln mit 1,1 mm Durchmesser. Tabelle 4: Zusammensetzung der expandierbaren Polymerpartikel (EPS) in Gewichtsanteilen und Eigenschaften der Schaumstoffformteile Beispiel 6 7 8 9 10 11 12 13 Zusammensetzung der expandierbaren Partikel Komponente A) 48 61 74 76,9 89,2 93 95,2 76,9 Komponente B1) 44 33 22 19,6 9,1 6,2 4,1 Komponente B2) 19,6 Komponente C) 8 6 4 3,5 1,7 1 0,8 3,5 Eigenschaften des Schaumstoffformteils Schaumstoffdichte [g/L] 27,5 25,3 20,2 20,0 19,9 20,1 20,4 20,1 Minimale Dichte [g/L] 23,9 21,7 16,7 17,0 15,5 15,0 14,5 17,0 Druckfestigkeit 10% [kPa] 84 97 97 96 98 93 93 91 Biegefestigkeit [kPa] 180 230 223 261 230 226 236 296 Biegearbeit [Nm] 2,1 5,8 3,4 3,9 3,7 3,2 2,8 4,0 Verformungsrest [%] 55 44 28 30 31 28 29 31 The small particle sizes 0.8 mm showed an improvement in the workability of the molding with respect to demolding and filling behavior of the tool. Additionally, the molding surface became more homogeneous than 1.1 mm diameter particles. Table 4: Composition of the expandable polymer particles (EPS) in parts by weight and properties of the foam moldings example 6 7 8th 9 10 11 12 13 Composition of the expandable particles Component A) 48 61 74 76.9 89.2 93 95.2 76.9 Component B1) 44 33 22 19.6 9.1 6.2 4.1 Component B2) 19.6 Component C) 8th 6 4 3.5 1.7 1 0.8 3.5 Properties of the foam molding Foam density [g / L] 27.5 25.3 20.2 20.0 19.9 20.1 20.4 20.1 Minimum density [g / L] 23.9 21.7 16.7 17.0 15.5 15.0 14.5 17.0 Compressive strength 10% [kPa] 84 97 97 96 98 93 93 91 Bending strength [kPa] 180 230 223 261 230 226 236 296 Bending work [Nm] 2.1 5.8 3.4 3.9 3.7 3.2 2.8 4.0 Deformation [%] 55 44 28 30 31 28 29 31

Claims (9)

  1. A thermoplastic particle foam which has cells having a mean cell size in the range from 20 to 500 µm, wherein the cell membranes have a nanocellular or fibrous structure having pore or fiber diameters below 1500 nm.
  2. The thermoplastic particle foam according to claim 1, wherein the mean pore or fiber diameter of the nanocellular or fibrous structure is in the range from 10 to 1000 nm.
  3. The thermoplastic particle foam according to claim 1 or 2, wherein the polymer matrix comprises a continuous phase which is rich in styrene polymer and a disperse polyolefin-rich phase.
  4. The thermoplastic particle foam according to any of claims 1 to 3, wherein the polymer matrix comprises
    A) from 45 to 98.9 percent by weight of styrene polymer,
    B) from 1 to 45 percent by weight of polyolefin and
    C) from 0.1 to 10 percent by weight of a hydrogenated or unhydrogenated styrene-butadiene block copolymer.
  5. A process for producing thermoplastic particle foams according to any of claims 1 to 4, which comprises
    a) producing a polymer mixture having a continuous phase and a disperse phase by mixing two incompatible thermoplastic polymers,
    b) impregnating this mixture with a blowing agent and pelletizing it to produce expandable thermoplastic polymer particles,
    c) prefoaming the expandable, thermoplastic polymer particles to produce foam particles and
    d) fusing the prefoamed foam particles in a mold by means of hot air or steam at a processing pressure which is kept sufficiently low for the nanocellular or fibrous structure in the cell membranes to be retained to produce particle foam moldings.
  6. A process for producing thermoplastic particle foams according to any of claims 1 to 4, which comprises
    a) producing a polymer mixture having a continuous phase and a disperse phase by mixing two incompatible thermoplastic polymers,
    b) pelletizing this mixture and after-impregnating it with a blowing agent in an aqueous phase under superatmospheric pressure at elevated temperature to produce expandable thermoplastic polymer particles,
    c) prefoaming the expandable, thermoplastic polymer particles to produce foam particles and
    d) fusing the prefoamed foam particles in a mold by means of hot air or steam at a processing pressure which is kept sufficiently low for the nanocellular or fibrous structure in the cell membranes to be retained to produce particle foam moldings.
  7. The process according to claim 5 or 6, wherein the mean diameter of the disperse phase of the polymer mixture is in the range from 1 to 1500 nm.
  8. The process according to any of claims 5 to 7, wherein the polymer mixture is produced in step a) by mixing
    A) from 45 to 98.9 percent by weight of styrene polymer,
    B) from 1 to 45 percent by weight of polyolefin and
    C) from 0.1 to 10 percent by weight of a hydrogenated or unhydrogenated styrene-butadiene block copolymer.
  9. The process according to any of claims 5 to 8, wherein from 1 to 10 percent by weight, based on the polymer mixture, of a C3-C8-hydrocarbon is used as blowing agent in step b).
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EP2144959A1 (en) 2010-01-20
BRPI0809543A2 (en) 2014-09-16
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ES2358307T3 (en) 2011-05-09
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JP5570413B2 (en) 2014-08-13
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UA97838C2 (en) 2012-03-26
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